Process for preparing thickened compositions



April 9, 1968 R. L. MCMILLEN PROCESS FOR PREPARING THICKBNEDCOMPOSITIONS Filed March 9, 1967 m R m m QO \w m L. lwv m m 0 (N 3 G o w0 VL A\ Ewiom \fiu m WN v if NN V 2 ems 8 Q amms mm Y2 \w C 2 vm ESEEP/E m AGENT United States Patent 3,377,283 PROCESS FOR PREPARINGTHICKENED COMPOSITIONS Richard L. McMillan, Painesville, Ohio, assignorto The lubrizol Corporation, Wicklitfe, Ohio, a corporation of bioContinuation-impart of application Ser. No. 369,271, May 21, 1964. Thisapplication Mar. 9, 1967, Ser. No. 621,825

15 Claims. (Cl. 252-33) ABSTRACT OF THE DISCLOSURE A process subject tocontinuous operation which comprises passing an alkali or alkaline earthmetal overbased organic material in admixture with a conversion agentthrough an elongated heating tube at a temperature within the range ofabout 90-320 C. and a pressure in excess of one atmosphere which issufficient to maintain the admixture in the liquid state. Oil solutionsof carbonated basic alkaline earth metal salts or complexes ofpetrosulfonic acids are typical overbased organic materials while water,carboxylic acids, and alcohols are among the suitable conversion agents.The products are non-Newtonian colloidial disperse systems which areuseful as lubricants, and additives for lubricants, resins, coatingcompositions, and the like.

This application is a continuation-in-part of copending application Ser.No. 369,271 filed May 21, 1964 now abandoned.

This invention relates to an improved process for pre paring colloidaldisperse systems. In a more particular sense it relates to an improvedprocess for preparing non- Newtonian colloidal disperse systems whichare characterized by a high degree of basicity and are useful aslubricants and as additives in lubricants, asphalts, fuels, cuttingoils, caulking compounds, polymeric compositions, corrosion preventingcoatings, etc.

In earlier filed application Ser. No. 185,521, filed Apr. 6, 1962, nowPatent No. 3,242,079, applicant described the manufacture of thesegrease-like colloidal disperse systems by the process of homogenizing anoil soluble solution of an overbased organic material (i.e., acarbonated alkaline earth metal salt of an oil-soluble acid) having ametal ratio of at least about 4.5 with, as the conversion agent, anactive hydrogen compound selected from the class consisting of loweraliphatic carboxylic acids, water, and water-alcohol mixtures at atemperature of between 25 C. and the reflux temperature of the mixture.In subequent applications, such as Ser. No. 309,293 filed Sept. 16,1963, Ser. No. 323,135 filed Nov. 12, 1963, Ser. No. 535,048 filed Mar.17, 1966, Ser. No. 535,742 filed Mar. 21, 1966, Ser. No. 535,693 filedMar. 21, 1966, Ser. No. 580,575 filed Sept. 20, 1966. Ser. No. 612,332filed Jan. 30, 1967.

Basically, these processes, as described in these earlier filedapplications, are carried out by vigorously stirring the mixture ofingredients, i.e., the overbased organic material and the conversionagent, while heating for a sufiicient time to effect conversion to thecolloidal disperse systems. Mechanical agitation of the mass becomesincreasingly difficult as the conversion process progresses since theresulting colloidal disperse system is more viscous than the initialmixture of ingredients. In order to obtain good mixing and to preventthe build-up of the thickened material on the walls of the vessel, it isusually necessary to employ an agitator having scraper blades whichclosely follow the walls of the vessel. Stirring of this nature requiresthe use of a powerful motor to drive the agitator. It is 3,377,283Patented Apr. 9, 1968 not uncommon to find that the agitator and the1000 gallon kettle must be driven by a twenty horsepower motor. I g

It has been found that the conversion process can be performed with agreat saving in time, power, and expensive equipment by passing themixture of ingredients in the proper proportions through an elongatedheating zone under suflicient pressure to maintain the mixture in aliquid state While heating it to a temperature within the range of fromabout 90 C., to about 320 C., and below the decomposition temperature ofthe least stable component in the mixture. v

Accordingly, it is anobject of this invention to provide an improvedprocess for preparing non-Newtonian colloidal disperse systems.

It is also an object of this invention to provide an improved processfor thepreparation of non-Newtonian colloidal disperse systems theprocess being capable of continuous operation. I

It is a further object of this invention to provide improved process forpreparing a non-Newtonian colloidal disperse system useful as lubricantsand as additives for lubricants, polymeric compositions, fuels, drawingcornpounds, and the like.

These and other objects of the invention are attained in accordance withthis invention by providing a process for converting a member selectedfrom the class consisting of alkali and alkaline earth metal overbasedorganic materials having a metal ratio of at least about 3.5, saidmaterial comprising at least about 30% by weight of nonmetal containingliquid medium, into a non-Newtonian colloidal disperse system comprisingpassing a mixture of (1) at least one said overbased organic materialand (2) from about 1% to about by weight based on the weight of saidoverbased organic material excluding the weight of the liquid medium ofa conversion agent selected from the class consisting of water, loweraliphatic carboxylic acids, aliphatic alcohols, cycloaliphatic alcohols,arylaliphatic alcohols, phenols, ketones, aldehydes, amines, boronacids, and phosphoric acids, through an elongated heating zone under apressure above one atmosphere and sufiicient to maintain the mixture inthe liquid state at a temperature within the range of from about C. toabout 320 C. at such a rate that an increment of said mixture is in theheating zone for a sufficient time to permit conversion to take place.

Referring now to the drawing, a diagrammatic representation of a typicalsystem which may be employed in the practice of this invention, rawmaterials consisting of an overbased organic material and a conversionagent are introduced, in the proper proportions, through line 1 into themixing tank 2 which is equipped with a stirrer means 3. Inertingredients may also be introduced into the conversion mixture. Saidinert ingredients may include inert liquids, particularly solvents forthe overbased organic material such as a hydrocarbon solvent (e.g., alow boiling petroleum naphtha) and/or a bodying agent such as apolystyrene or other resin to modify the characteristics of the finishedproduct. Preferably the resins will be soluble in the conversionmixture.

After thorough mixing is accomplished in tank 2, the conversion mixtureis passed through valved line 4 to the high pressure pump 5, and thenthrough line 6-,check valve 10, and vale 12 to the elongated heatingzone 13. Line 6 is also connected through a surge tank 7 to a pressureswitch 8 Which is set to cut off the pump motor at a pre-determinedmaximum pressure. Line 6, as a safety measure, is also connected to apressure relief valve 9.

The mixture, while passing through the elongated heating zone 13, isheated to the desired temperature and is held at that temperature for asuflicient period of time to permit gelling of the product to takeplace. The mixture within the heating zone 13 is maintained undersufficient pressure to keep the volatile components in the liquid stateby the high pressure pump 5 which is regulated by the pressure switch 8and the back pressure regulator 16.

The product from the heated zone 13 passes through line 14, equippedwith a surge tank 15, to the back pressure regulator 16 and then throughvalved line 17 to the receiver tank 19. Alternatively, the product maybe drawn off through valve 18. Provision is made to heat line 14, surgetank 15, back-pressure regulator 16 and line 17 by steam jacketing.

Upon passing from the high pressure side to the low pressure side of thepressure regulator 16, much of the conversion agent, if volatile, andvolatile inert solvents, if used, are vaporized from the hot product. Itfurther removal of the conversion agent or volatile solvents is desired,one means for accomplishing this is to pass the product into thereceiver tank 19 where it may be diluted with a solvent introducedthrough line 21. The additional solvent, if employed, may be a lowboiling petroleum fraction to reduce the viscosity of the product andaid in drying the product by azeotropic distillation. The product mayalso be diluted with a mineral oil or other suitable organic liquids toreduce the viscosity of the reaction product.

The conversion agent, if volatile, may be removed from the gelledproduct by heating it in receiver tank 19 with agitation provided bystirrer 20. Overhead vapors from receiver tank 19 are passed to column23 via line 22 and then via line 24 to condenser 25. Condensed vaporspass from the condenser 25 through line 26 to the receiver 27 which maybe vented to the atmosphere or attached to a vacuum line by means ofvalved line 28. The condensate passes through line 29 from the receiver27 to a liquid phase separator 30 from which the conversion agents maybe drawn off via valved line 31. If a volatile solvent, which isimmiscible with the conversion agent, is used to dilute the product inthe receiver tank 19 as an aid in removal of the conversion agent byazeotropic distillation, the volatile solvent may be separated in theliquid phase separator 30 and returned to the receiver tank 19 by way ofvalved line 32. The solvent may also be drawn off with the conversionagent through valved line 31.

Nitrogen or other inert gas may be passed through the product inreceiver tank 19 via submerged line 33 in order to help free the productof the conversion agent and/or the solvent if such removal is desired.The finished product is removed from the product receiver tank 19 viavalved line 34.

Preparing colloidal disperse systems by the process of this invention iseffected by passing a mixture of the ingredients in the appropriateproportions through the elongated heating zone 13 under sufiicientpressure to maintain all of the reactants in the liquid state. Thepressure required, of course, varies with the temperature of theconversion process and the components of the conversion mixture and mayrange :from only slightly above atmospheric pressure to several hundredpounds per square inch. The temperature at which the conversion processis carried out is preferably above about 90 C. and below about 320 C. orthe decomposition temperature of the least stable component of thereaction mixture. The rate at which the conversion mixture is passedthrough the gelling unit is also dependent on the temperature at whichthe process is carried out and the residence time of the reactionmixture in the heated reaction zone may vary from several hours at lowreaction temperature to as little as one minute or less at the uppertemperature limit.

When preparing the non-Newtonian colloidal disperse system by passingthe conversion mixtures through the heated elongated. tube underpressure, it should be apparent to those skilled in the art that anysolid components are not to be converted to the liquid state in theliteral sense. Rather, any solid components going into the conversionmixture are either dissolved in the mixture or are mixed therewith anduse the liquid portion of the mixture as a vehicle in which they arepassed through the heating zone. Thus, the pressure used is intended tomaintain all or substantially all of the liquid components of theconversion mixture in the liquid state.

The ovenbased organic materials and the conversion agents necessary forpreparing the colloidal disperse systems produced by the process of thisinvention are discussed in detail in applicants above-identified earlierfiled applications and patent. Since the present invention involveseffecting conversion of the overbased organic materials by passing theingredients through the elongated tube under specified conditions oftemperature and pressure in lieu of the previously indicated vigorousand sometimes prolonged mechanical stirring, these prior disclosures ofidentity, preparation, and relative amounts of overbased organicmaterials and conversion agents accurately describe the necessarycompounds and amounts of materials which are to be the components of themixtures to be converted to non-Newtonian colloidal disperse systemsaccording to the present process. Thus, these earlier filed applicationsand patent are incorporated herein by reference. It will be understoodby those skilled in the art that any of the overbased organic materialsand any of the conversion agents (except oxygen, air, and carbondioxide) can be mixed in the proportions indicated in these earlierapplications and converted to a colloidal disperse system according tothe process of the present application.

The earlier filed applications and the patent also disclose various usesfor the non-Newtonial colloidal disperse systems and give actualexamples demonstrating how they may be used such as protective coatingsfor metal surfaces, lubricants, and additives for polymericcompositions. Accordingly, these applications and the patent areincorporated herein by reference thereto for the benefit of theirdisclosures regarding the utility of the products produced by thepresent process.

The disperse systems, the overbased organic starting material, and theconversion agents are discussed below:

THE COLLOIDAL DISPERSE SYSTEMS The terminology disperse system as usedin the specification and claims is a term of art generic to colloids orcolloidal solutions, e.g., any homogeneous medium containing dispersedentities of any size and state, B. Jirgensons and M. E. Straumanis, AShort Textbook on Colloidal Chemistry (2nd ed.), The Macmillan Co.,N.Y., 1962, pages 1 and 178 through 183 in particular. However, theparticular disperse systems of the present invention form a subgenuswithin this broad class of disperse systems, this subgenus beingcharacterized by several important features.

This subgenus comprises those disperse systems wherein at least aportion of the particles dispersed therein are solid, metal-containingparticles formed in situ. At least about 10% to about 50% are particlesof this type and preferably, substantially all of said solid particlesare formed in situ.

So long as the solid particles remain dispersed in the dispersing mediumas colloidal particles the particle size is not critical. Ordinarily,the particles will not exceed 5000 A. However, it is preferred that themaximum unit particle size be less than about 1000 A. In a particularlypreferred aspect of the invention, the unit particle size is less thanabout 400 A. Systems having a unit particle size in the range of 30 A.to 200 A. give excellent results. The minimum unit particle size is atleast 20 A. and preferably at least about 30 A. I

The language unit particle size is intended to designate the averageparticle size of the solid, metal-containing particles assuming maximumdispersion of the individual particles throughout the disperse medium.That is, the unit particle is that particle which corresponds in size tothe average size of the metal-containing particles and is capable ofindependent existence Within the disperse system as a discrete colloidalparticle. These metalcontaining particles are found in two forms in thedisperse systems. Individual unit particles can be dispersed as suchthroughout the medium or unit particles can form an agglomerate, incombination With other materials (e.g., another metal-containingparticle, the disperse medium, etc.) which are present in the dispersesystems. These agglomerates are dispersed through the system asmetalcontaining particles. Obviously, the particle size of theagglomerate is substantially greater than the unit particle size.Furthermore, it is equally apparent that this agglomerate size issubject to Wide variations, even within the same disperse system. Theagglomerate size varies, for example, with the degree of shearing actionemployed in dispersing the unit particles. That is, mechanical agitationof the disperse system tends to break down the agglomerates into theindividual components thereof and disperse these individual componentsthroughout the disperse medium. The ultimate in dispersion is achievedwhen each solid, metal-containing particle is individually dispersed inthe medium. Accordingly, the disperse systems are characterized withreference to the unit particle size, it being apparent to those skilledin the art that the unit particle size represents the average size ofsolid, metal-containing particles present in the system which can existindependently. The average particle size of the metal-containing solidparticles in the system can be made to approach the unit particle sizevalue by the application of a shearing action to the existent system orduring the formation of the disperse system as the particles are beingformed in situ. It is not necessary that maximum particle dispersionexist to have useful disperse systems. The agitation associated withhomogenization of the overbased material and conversion agent producessufficient particle dispersion.

Basically, the solid metal-containing particles are in the form of metalsalts of inorganic acids and low molecular weight organic acids,hydrates thereof, or mixtures of these. These salts are usually thealkali and alkaline earth metal forrnates, acetates, carbonates,hydrogen carbonates, hydrogen sulfides, sulfites, hydrogen sulfites, andhalides, particularly chlorides. In other Words, the metalcontainingparticles are ordinarily particles of metal salts, the unit particle isthe individual salt particle and the unit particle size is the averageparticle size of the salt particles which is readily ascertained, as forexample, by conventional X-ray defraction techniques. Colloidal dispersesystems possessing particles of this type are sometimes referred to asmacromolecular colloidal systems.

Because of the composition of the colloidal disperse systems of thisinvention, the metal-containing particles also exist as components inmicellar colloidal particles. In addition to the solid metal-containingparticles and the disperse medium, the colloidal disperse systems of theinvention are characterized by a third essential component, one which issoluble in the medium and contains in the molecules thereof ahydrophobic portion and at least one polar substituent. This thirdcomponent can orient itself along the external surfaces of the abovemetal salts, the polar groups lying along the surface of these saltswith the hydrophobic portions extending from the salts into the dispersemedium forming micellar colloidal particles. These micellar colloids areformed through weak intermolecular forces, e.g., Van der Waals forces,etc. Micellar colloids represent a type of agglomerate particle asdiscussed hereinabove. Because of the molecular orientation in thesemicellar colloidal particles, such particles are characterized by ametal containing layer (i.e., the solid metal-containing particles andany metal present in the polar substituent of the third component, suchas the metal in a sulfonic or carboxylic acid salt group), a hydrophobiclayer formed by the hydrophobic portions of the molecules of the thirdcomponent and a polar layer bridging said metal-containing layer andsaid hydrophobic layer, said polar bridging layer comprising the polarsubstituents of the third component of the system, e.g., the

group if the third component is an alkaline earth metal petrosulfonate.

The second essential component of the colloidal disperse system is thedispersing medium. The identity of the medium is not a particularlycritical aspect of the invention as the medium primarily serves as theliquid vehicle in which solid particles are dispersed. The dispersemedium will normally consist of inert organic liquids, that is, liquidswhich are chemically substantially inactive in the particularenvironment in question (the resinous composition). While many of theseinert organic liquids are nonpolar, this is not essential. For example,many of the plasticizers for the resinous components of the compositionare esters, etc. These polar materials can also be used as thedispersing medium or components thereof. The medium can have componentscharacterized by relatively low boiling points, e.g., in the range of 25to C. to facilitate subsequent removal of a portion or substantially allof the medium from the polymeric resin composition or the components canhave a higher boiling point to protect against removal from the resinouscomposition upon standing or heating. Obviously, there is no criticalityin an upper boiling point limitation on these liquids.

Representative liquids include the alkanes and haloalkanes of five toeighteen carbons, polyhaloand perhaloalkanes of up to about six carbons,the cycloalkanes of five or more carbons, the corresponding alkyland/orhalo-substituted cycloalkanes, the aryl hydrocarbons, the alkylarylhydrocarbons, the haloaryl hydrocarbons, ethers such as dialkyl ethers,alky aryl ethers, cycloalkyl ethers, cycloalkylalkyl ethers, alkanols,alkylene glycols, polyalkylene glycols, alkyl ethers of alkylene glycolsand polyalkylene glycols, dimethyl formamide, dimethyl acetamide,dibasic alkanoic acid diesters, silicate esters, and mixtures of these.Specific examples include petroleum ether, Stoddard solvent, pentane,hexane, octane, isooctane, undecane, tetradecane, cyclopentane,cyclohexane, isopropylcyclohexane, 1,4-dimethylcyclohexane, cyclooctane, benzene, toluene, xylene, ethyl benzene, tertbHtYl-b6I1Z6I16,halobenzenes especially monoand polychlorobenzenes such as chlorobenzeneper se and 3,4-dichlorotoluene, mineral oils, n-propylether,isopropylether, isobutylether, n-amylether, methyl-n-butylethe'r,methyln-amyl-ether, cyclohexylether, ethoxycyclohexane, methoxybenzene,isopropoxybenzene, p-methoxytoluene, methanol, ethanol, propanol,iso-propanol, hexanol, n-octyl alcohol, n-decyl alcohol, alkyleneglycols such as ethylene glycol and propylene glycol, diethyl ketone,dipropyl ketone, methylbutyl ketone, acetophenone,1,2-difluorotetrachloroethane, dichlorofluoromethane,1,2-dibrometetrafluoroethane, trichlorofluoromethane, l-chloropentane,1,3-dich1orohexane, formamide, dimethylformamide, acetamide,dimethylacetamide, diethylacetamide, propionamide, di-isooctyl azelate,ethylene glycol, polypropylene glycols, hexa-Z-ethylbutoxy disiloxane,etc.

Also useful as dispersing mediums are the low molecular Weight, liquidpolymers, generally classified as oligomers, which include the dimers,tetramers, phentamers, etc. 11- lustrative of this large class ofmaterials are such liquids as the propylene tetramers, isobutylenedimers, and the like.

From the standpoint of availability, cost, and performance, the alkyl,cycloalkyl, and aryl hydrocarbons represent a preferred class ofdisperse mediums. Liquid petroleum fractions represent another preferredclass of disperse mediums. Included within these preferred classes arebenzenes and alkylated benzers, cycloalkanes and alkylated cycloalkanes,cyclo-alkenes and alkylated cycloalkenes such as found innaphthene-based petroleum fractions, and the alkanes such as found inthe paraffinbased petroleum fractions. Petroleum ether, naphthas,mineral oils, Stoddard solvent, toluene, xylene, etc., and mixturesthereof are examples of economical sources of suitable inert organicliquids which can function as the disperse medium in the colloidaldisperse systems of the present invention.

The most preferred disperse systems are those containing at least somemineral oil as a component of the disperse medium. These systems areparticularly eifective as lubricants for the polymeric composition, animportant feature in extrusion processes. Any amount of mineral oil isbeneficial in this respect. However, in this preferred class of systems,it is desirable that mineral oil comprise at least about 1% by weight ofthe total medium, and preferably at least about 5% by Weight. Thosemediums comprising at least by weight mineral oil are especially useful.As will be seen hereinafter, mineral oil can serve as the exclusivedisperse medium.

In addition to the solid, metal-containing particles in the dispersemedium, the two essential elements of any disperse system, the dispersesystems employed in the polymeric compositions of the invention requirea third essential component. This third component is an organic compoundwhich is soluble in the disperse medium, and the molecules of which arecharacterized by a hydrophobic portion and at least one polarsubstituent. As explained, infra, the organic compounds suitable as athird component are extremely diverse. These com-pounds are inherentconstituents of the disperse systems as a result of the methods used inpreparing the systems. Further characteristics of the components areapparent from the following discussion of methods for preparing thecolloidal disperse systems.

PREPARATION OF THE DISPERSE SYSTEMS Broadly speaking, the colloidaldisperse systems of the invention are prepared by treating a singlephase homogeneous, Newtonian system of an overbased, superbased, orhyperbased, organic compound with a conversion agent, usually an activehydrogen containing compound, the treating operation being simply athorough mixing together of the two components, i.e., homogenization.This treatment converts these single phase systems into thenon-Newtonian colloidal disperse systems utilized in conjunction withthe polymeric resins of the present invention.

The terms overbased, superbased, and hyperbased, are terms of art whichare generic to well-known classes of metal-containing materials whichhave generally been employed as detergents and/ or dispersants inlubricating oil compositions. These overbased materials have also beenreferred to as complexes, metal complexes, high-metal containing salts,and the like. Overbased materials are characterized by a metal contentin excess of that which would be present according to the stoichiometryof the metal and the particular organic compound reacted with the metal,e.g., a carboxylic or sulfonic acid. Thus, if a monosulfonic acid,

is neutralized with a basic metal compound, e.g., calcium hydroxide, thenormal" metal salt produced will contain one equivalent of calcium foreach equivalent of acid, i.e.,

However, as'is well-known in the art, various processes are availablewhich result in an enert organic liquid solution of a product containingmore than the stoichiometric amount of metal. The solutions of theseproducts are referred to herein as overbased materials. Following theseprocedures, the sulfonic acid or an alkali or alkaline earth metal saltthereof can be reacted with a metal base and the product will contain anamount of metal in excess of that necessary to neutralize the acid, forexample, 4.5 times as much metal as present in the normal salt of ametal excess of 3.5 equivalents. The actual stoichiometric excess ofmetal can vary considerably, for example, from about 0.1 equivalent toabout 30 or more equivalents depending on the reactions, the processconditions, and the like. These overbased materials useful in preparingthe disperse systems will contain from about 3.5 to about 30 or moreequivalents of metal for each equivalent of material which is overbased.

In the present specification and claims the term overbased" is used todesignate materials containing a stoichiometric excess of metal and is,therefore, inclusive of those materials which have been referred to inthe art as overbased, superbased, hyperbased, etc., as discussed supra.

The terminology metal ratio is used in the prior art and herein todesignate the ratio of the total chemical equivalents of the metal inthe overbased material (e.g., a metal sulfonate or carboxylate) to thechemical equivalents of the metal in the product which would be expectedto result in the reaction between the organic material to be overbased(e.g., sulfonic or carboxylic acid) and the metal-containing reactant(e. g., calcium hydroxide, barium oxide, etc.) according to the knownchemical reactivity and stoichiometry of the two reactants. Thus, thenormal calcium sulfonate discussed above, the metal ratio is one and inthe overbased sulfonate, the metal ratio is 4.5. Obviously, if there ispresent in the material to be overbased more than one compound capableof reacting with the metal, the metal ratio of the product will dependupon whether the number of equivalents of metal in the overbased productis compared to the number of equivalents expected to be present for agiven single component or a combination of all such components.

Generally, these overbased materials are prepared by treating a reactionmixture comprising the organic material to be overbased, a reactionmedium consisting essentially of at least one, an inert, organic solventfor said organic material, a stoichiometric excess of a metal base, anda promotor with an acidic material. The methods for preparing theoverbased materials as well as an extremely diverse group of overbasedmaterials are well-known in the prior art and are disclosed, for examplein the following US. patents: 2,616,904, 2,616,905, 2,616,906, 2,616,-911, 2,616,924, 2,616,925, 2,617,049, 2,695,910, 2,723,- 234, 2,723,235,2,723,236, 2,760,970, 2,767,164, 2,767,- 209, 2,777,874, 2,798,852,2,839,470, 2,856,359, 2,856,- 360, 2,856,361, 2,861,951, 2,883,340,2,915,517, 2,959,- 551, 2,968,642, 2,971,014, 2,989,463, 3,001,981,3,027,- 325, 3,070,581, 3,108,960, 3,147,232, 3,133,019, 3,146,- 201,3,152,991, 3,155,616, 3,170,880, 3,170,881, 3,172,- 855, 3,194,823,3,223,630, 3,232,883, 3,242,079, 3,242,- 080, 3,250,710, 3,256,186,3,274,135. The disclosures of these patents disclose exemplary processesfor synthesizing the overbased materials used in producing the dispersesystems of the invention and are, accordingly, incorporated herein byreference for their disclosures of these processes, materials which canbe overbased, suitable metal bases, promoters, and acidic materials, aswell as a variety of specific overbased products.

An important characteristic of the organic materials which are overbasedis their solubility in the particular reaction medium utilized in theoverbasing process. As the reaction medium used previously has normallycomprised petroleum fractions, particularly mineral oils, these organicmaterials have generally been oil-soluble. However, if another reactionmedium is employ (eQg., aromatic hydrocarbons, aliphatic hydrocarbons,kerosene, etc.) it is not essential that the organic material be solublein mineral oil as long as it is soluble in the given reaction medium.Obviously, many organic materials which are soluble in mineral oils willbe soluble in many of the other indicated suitable reaction mediums. Itshould be apparent that the reaction medium usually becomes the dispersemedium of the colloidal disperse system or at least a component thereofdepending on whether or not additional inert organic liquid is added aspart of the reaction medium or the disperse medium.

Materials which can be overbased are generally oilsoluble organic acidsincluding phosphorus acids, thiophosphorus acids, sulfur acids,carboxylic acids, thiocarboxylic acids, and the like, as well as thecorresponding alkali and alkaline earth metal salts thereof.Representative examples of each of these classes of organic acids aswell as other organic acids, e.g., nitrogen acids, arsenic acids, etc.are disclosed along with methods, of preparing overbased productstherefrom in the above cited patent and are, accordingly, incorporatedherein by reference. Patent 2,777,874 identifies organic acids suitablefor preparing overbased materials which can be converted to dispersesystems for use in the resinous compositions of the invention.Similarly, 2,616,904, 2,695,- 910, 2,767,164, 2,767,209, 3,147,232,3,274,135, etc. disclose a variety of organic acids suitable forpreparing overbased materials as well as representative examples ofoverbased products prepared from such acids. Overbased acids wherein theacid is a phosphorus acid, a thiophosphorus acid, phosphorus acid-sulfuracid combination, and sulfur acid prepared from polyolefins aredisclosed in 2,883,340, 2,915,517, 3,001,981, 3,108,960, and 3,232,883.Overbased phenates are disclosed in 2,959,551 while overbased ketonesare found in 2,798,852. A variety of overbased materials derived fromoil-soluble metalfree, non-tautomeric neutral and basic organic polarcompounds such as esters, amines, amides, alcohols, ethers, sulfides,sulfoxides, and the like are disclosed in 2,968,- 642, 2,971,014, and2,989,463. Another class of materials which can be overbased are theoil-soluble, nitro-substituted aliphatic hydrocarbons, particularlynitro-substituted polyolefins such as polyethylene, polypropylene,polyisobutylene, etc. Materials of this type are illustrated in2,959,551. Likewise, the oil-soluble reaction product of alkylenepolyamines such as propylene diamine or N- alkylated propylene diaminewith formaldehyde or formaldehyde producing compound (e. g.,paraformaldehyde) can be overbased. Other compounds suitable foroverbasing are disclosed in the above-cited patents or are otherwisewell-known in the art.

The organic liquids used as the disperse medium in the colloidaldisperse system can be used as solvents for the overbasing process.

The metal compounds used in preparing the overbased materials arenormally the basic salts of metals in Group I-A and Group II-A of thePeriodic Table although other metals such as lead, zinc, manganese, etc.can be used in the preparation of overbased materials. The anionicportion of the salt can be hydroxyl, oxide, carbonate, hydrogencarbonate, nitrate, sulfite, hydrogen sulfite, halide, amide, sulfateetc. as disclosed in the above-cited patents. For purposes of thisinvention the preferred overbased materials are prepared from thealkaline earth metal oxides, hydroxides, and alcoholates such as thealkaline earth metal lower alkoxides. The most preferred dispersesystems of the invention are made from overbased materials containingcalcium and/or barium as the metal.

The promoters, that is, the materials which permit the incorporation ofthe excess metal into the overbased material, are also quite diverse andwell-known in the art as evidenced by the cited patents. A particularlycomprehensive discussion of suitable promoters is found in 2,777,874;2,695,910; and 2,616,904. These include the alcoholic and phenolicpromoters which are preferred.

The alcoholic promoters include the alkanols of one to about twelvecarbon atoms such as methanol, ethanol, amyl alcohol, octanol,isopropanol, and mixtures of these and the like. Phenolic promotersinclude a variety of hydroxy-substituted benzenes and naphthalenes. Aparticularly useful class of phenols are the alkylated phenols of thetype listed in 2,777,874, e.g., heptylphenoles, octylphenols, andnonylphenols. Mixtures of various promoters are sometimes used.

Suitable acidic materials are also disclosed in the above cited patents,for example, 2,616,904. Included within the known group of useful acidicmaterials are liquid acids such as formic acid, acetic acid, nitrictacid, sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid,substituted carbamic acids, etc. Acetic acid is a very useful acidicmaterial although inorganic acidic materials such as HCl, S0 S0 CO H 8,N 0 etc., are ordinarily employed as the acidic materials. The mostpreferred acidic materials are carbon dioxide and acetic acid.

In preparing overbased materials, the material to be overbased, aninert, non-polar, organic solvent therefor, the metal base, thepromoter, and the acidic material are brought together and a chemicalreaction ensues. The exact nature of the resulting overbased product isnot known. However, it can be adequately described for purposes of thepresent specification as a single phase homogeneous mixture of thesolvent and (1) either a metal complex formed from the metal base, theacidic material, and the material being overbased and/or (2) anarmorphous metal salt formed from the reaction of the acidic materialwith the metal base and the material which is said to be overbased.Thus, if mineral oil is used as the reaction medium, petrosulfonic acidas the material which is overbase d, Ca(OH) as the metal base, andcarbon dioxide as the acidic material, the resulting overbased materialcan be described for purposes of this invention as an oil solution ofeither a metal containing a complex of the acidic material, the metalbase, and the petrosulfonic acid or as an oil solution of amorphouscalcium carbonate and calcium petrosulfonate. Since the overbasedmaterials are well-known and as they are used merely as intermediates inthe preparation of the disperse systems employed herein, the exactnature of the materials is not critical to the present invention.

The temperature at which the acidic material is contacted with theremainedr of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about C. to 300 C., and preferably from about C. to about200 C. When an alcohol or mercaptain is used as the promoting agent, thetemperature usually will not exceed the reflux temperature of thereaction mixture and preferably will not exceed about 100 C.

In view of the foregoing, it should be apparent that the overbasedmaterials may retain all or a portion of the promoter. That is, if thepromoter is not volatile (e.g., an alkyl phenol) or otherwise readilyremovable from the overbased material, at least some promoter remains inthe overbased product. Accordingly, the disperse systems made from suchproducts may also contain the promoter. The presence or absence of thepromoter in the overbased material used to prepare the disperse systemand likewise, the presence or absence of the promoter in the colloidaldisperse systems themselves does not represent a critical aspect of theinvention. Obviously, it is within the skill of the art to select avolatile promoter such as a lower alkanol, e.g., methanol, ethanol,etc., so that the promoter can be readily removed prior to forming thedisperse system or thereafter.

A preferred class of overbased materials used as starting materials inthe preparation of the disperse systems of the present invention are thealkaline earth metaloverbased oil-soluble organic acids, preferablythose containing at least twelve aliphatic carbons although the acidsmay contain as few as eight aliphatic carbon atoms if the acid moleculeincludes an aromatic ring such as phenyl, naphthyl, etc. Representativeorganic acids suitable for preparing these overbased materials arediscussed and identified in detail in the above-cited patents.Particularly 2,616,904, and 2,777,874 disclose a variety of verysuitable organic acids. For reasons of economy and performance,overbased oil-soluble carboxylic and sulfonic acids are particularlysuitable. Illustrative of the carboxylic acids are palmitic acid,stearic acid, myristic acid, oleic acid, linoleic acid, behenic acid,hexatriacontanoic acid, tetrapropylene-substituted glutaric acid,polyisobutene (M.W.5000)-substituted succinic acid, polypropylene(M.W.-l0,000)-substituted succinic acid, octadecyl-substituted adipicacid, chlorostearic acid, 9- rnethyl-stearic acid, dichlorostearic acid,stearylbenzoic acide, eicosane-substituted naphthoic acid,dilauryl-decahydronaphthalene carboxylic acid, didodecyl-tetralincarboxylic acid, dioctyl-cyclohexane carboxylic acid, mixtures of theseacids, their alkali and alkaline earth metal salts, and/or theiranhydrides. Of the oil-soluble sulfonic acids, the mono-, di-, andtri-aliphatic hydrocarbon substituted aryl sulfonic acids and thepetroleum sulfonic acids (petrosulfonic acids) are particularlypreferred. Illustrative examples of suitable sulfonic acids includemahogany sulfonic acids, petrolatum sulfonic acids,mono-eicosane-substituted naphthalene sulfonic acids, dodecylbenzenesulfonic acids, didodecylbenezene sultonic acids, dinonylbenzenesulfonic acids, cetyl-chlorobenzene sulfonic acids, dilaurylbeta-napthalene sulfonic acids, the sulfonic acid derived by thetreatment of polyisobutene having a molecular Weight of 1500 withchlorosulfonic acid, nitronaphthalene-sulfonic acide, parafiin Waxsulfonic acid, cetyl-cyclopentane sulfonic acid,lauryl-cyclohexanesulfonic acids, polyethylene (M.W.- 750) sulfonicacids, etc. Obviously, it is necessary that the size and number ofaliphatic groups on the aryl sulfonic acids be sufficient to render theacids soluble. Normally the aliphatic groups will be alkyl and/oralkenyl groups such that the total number of aliphatic carbons is atleast twelve.

Within this preferred group of overbased carboxylic and sulfonic acids,the barium and calcium overbased mono-, di-, and trialkylated benzeneand naphthalene (including hydrogenated forms thereof), petrosulfonicacids, and higher fatty acids are especially preferred. Illustrative ofthe synthetically produced alkylated benzene and naphthalene sulfonicacids are those containing alkyl substituents having from 8 to about 30carbon atoms therein. Such acids include di-isododecyl-benzene sulfonicacid, wax-substituted phenol sulfonic acid, wax-substituted benzenesulfonic acids, polybutene-substituted sulfonic acid,cetyl-chlorobenzene sulfonic acid, di-cetylnaphthalene sulfonic acid,di-lauryldiphenylether sulfonic acid, diisononylbenzene sulfonic acid,di-isooctadecylbenzenesulfonic acid, stearylnaphthalene sulfonic acid,and the like. The petroleum sulfonic acids are Well-known art recognizedclass of materials which have been used as starting materials inpreparing overbased products since the inception of overbasingtechniques as illustrated by the above patents. Petroleum sulfonic acidsare obtained by treating refined or semi-refined petroleum oils withconcentrated or turning sulfuric acid. These acids remain in the oilafter the settling out of sludges. These petrolcum sulfonic acids,depending on the nature of the petroleum oils from which they areprepared, are oil-soluble alkane sulfonic acids, alkyl-substitutedcycloaliphatic sulionic acids including cycloalkyl sulfonic acids andcycloalkene sulfonic acids, and alkyl, alkaryl, or aralkyl substitutedhydrocarbon aromatic sulfonic acids including single and condensedaromatic nuclei as well as partially hydrogenated forms thereof.Examples of such petrosulfonic acids include mahogany sulfonic acid,white oil sulfonic acid, petrolatum sulfonic acid, petroleum naphthenesulfonic acid, etc. This especially preferred group of aliphatic fattyacids includes the saturated and unsaturated higher fatty acidscontaining from 12 to about 30 carbon atoms. Illustrative of these acidsare lauric acid, palmitic acid, oleic acid, linoleic acid, linolenicacid, oleostearic acid, stearic acid, myristic acid, and undecalinicacid, alpha-chlorostearic acid and alpha-nitrolauric acid.

As shown by the representative examples of the preferred classes ofsulfonic and carboxylic acids, the acids may contain non-hydrocarbonsubstituents such as halo, nitro, alkoxy, hydroxyl, and the like.

It is desirable that the overbased materials used to prepare thedisperse system have a metal ratio of at least 3.5 and preferably about4.5 An especially suitable group of the preferred sulfonic acid overbasematerials has a metal ratio of at least about 7.0. While overbasematerials having a metal ratio of 75 have been prepared, normally themaximum metal ratio will not exceed about 30 and, in most cases not morethan about 20.

The overbased materials used in preparing the colloidal disperse systemscontain from about 10% to about 70% by weight of metal containingcomponents. As explained hereafter, the exact nature of these metalcontaining components is not known. It is theorized that the metal base,the acidic material, and the organic material being overbased form ametal complex, this complex being the metal-containing component of theoverbased material. On the other hand, it has also been postulated thatthe metal base and the acidic material form amorphous metal compoundswhich are dissolved in the inert organic reaction medium and thematerial which is said to be overbased. The material which is overbasedmay itself be a metal-containing compound, e.g., a carboxylic orsulfonic acid metal salt. In such a case, the metal-containingcomponents of the overbased material would be both the amorphouscompounds and the acid salt. The exact nature of these overbasedmaterials is obviously not critical in the present invention since thesematerials are used only as intermediates. The remainder of the overbasedmaterials consist essentially of the inert organic reaction medium andany promoter which is not removed from the overbased product. Forpurposes of this application, the organic material which is subjected tooverbasing is considered a part of the metal containing components.Normally, the liquid reaction medium constitutes at least about 30% byweight of the reaction mixture utilized to prepare theoverbasedmaterials.

As mentioned above, the colloidal disperse system can be prepared byhomogenzing a conversion agent and the overbased starting material.Homogenization is achieved by vigorous agitation of the two components,preferably at the reflux temperature or a temperature slightly below thereflux temperature. The reflux temperature normally will depend upon theboiling point of the conversion agent. However, homogenization may beachieved within the range of about 25 C. to about 200 C. or slightlyhigher. Usually, there is no real advantage in exceeding 150 C. Theprocess of the present invention replaces this batch process.

The concentration of'the conversion agent necessary to achieveconversion of the overbased material is usually within the range of fromabout 1% to about based upon the weight of the overbased materialexcluding the weight of the inert, organic solvent and any promoterpresent therein. Preferably at least about 10% and usually less thanabout 60% by weight of the conversion agent is employed. Concentrationsbeyond 60% appear to af ford no additional advantages.

The terminology conversion agent as used in the specification and claimsis intended to describe a class of very diverse materials which possessthe property of being able to convert the Newtonian homogeneous,singlephase, overbased materials into non-Newtonian colloidal dispersesystems. The mechanism 'by which conversion is accomplished is notcompletely understood. However, with the exception of oxygen, carbondioxide, air and mixtures of two or more of these, these conversionagents all possess active hydrogens. The conversion agents include loweraliphatic carboxylic acids, water, aliphatic alcohols, cycloaliphaticalcohols, arylaliphatic alcohols, phenols, ketones, aldehydes, amines,boron acids, phosphorus acids, oxygen, air, and carbon dioxide. Mixturesof two or more of these conversion agents are also useful. Particularlyuseful conversion agents are discussed below.

The lower aliphatic carboxylic acids are those containing less thanabout eight carbon atoms in the molecule. Examples of this class ofacids are formic acid, acetic acid, propionic acid, butyric acid,valeric acid, isovaleric acid, isobutyric acid, caprylic acid, heptanoicacid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.Formic acid, acetic acid, and propionic acid, are preferred with aceticacid being especially suitable. It is to be understood that theanhydrides of these acids are also useful and, for the purposes of thespecification and claims of this invention, the term acid in intended toinclude both the acid per se and the anhydride of the acid.

Useful alcohols include aliphatic, cycloaliphatic, and arylaliphaticmonoand polyhydroxy alcohols. Alcohols having less than about twelvecarbons are especially useful while the lower alkanols, i.e., alkanolshaving less than about eight carbon atoms are preferred for reasons ofeconomy and effectiveness in the process. Illustrative are the alkanolssuch as methanol, ethanol, isopropanol, npropanol, isobutanol, tertiarybutanol, isooctanol, dodecanol, n-pentanol, etc., cycloalkyl alcoholsexemplified by cyclopentanol, cyclohexanol, 4-methylcyclohexanol,2-cyclohexylethanol, cyclopentylmethanol, etc.; phenyl aliphaticalkanols such as benzyl alcohol, Z-phenylethanol, and cinnamyl alcohol;alkylene glycols of up to about six carbon atoms and mono-lower alkylethers thereof such as monoethylether of ethylene glycol, diethyleneglycol, ethylene glycol, trimethylene glycol, hexamethylene glycol,triethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol, andpentaery-thritol.

The use of a mixture of water and one or more of the alcohols isespecially effective for converting the overbased materials to colloidaldisperse systems. Such combinations often reduce the length of timerequired for the process. Any water-alcohol combination is effective buta very effective combination in a mixture of one or more alcohols andwater in a weight ratio of alcohol to water of from about 0.05:1 toabout 24:1. Preferably, at least one lower alkanol is present in thealcohol component of these water-alkanol mixtures. Water-alkanolmixtures wherein the alcoholic portion is a mixture of two or more loweralkanols, particularly methyl alcohol, ethyl alcohol, propyl alcohols,butyl alcohols, and pentyl alcohols, are especially suitable.Alcohol:water conversions are illustrated in copending application Ser.No. 535,693, filed Mar. 21, 1966.

Phenols suitable for use as conversion agents include phenol, n-aphthol,ortho-cresol, para-cresol, catechol, mixtures of cresol,para-tert-butylphenol, and other lower alkyl substituted phenols,meta-polyisobutene(M.W.- 350)-substituted phenol, and the like.

Other useful conversion agents include lower aliphatic aldehydes andketones, particularly lower alkyl aldehydes and lower alkyl ketones suchas acetaldehydes. propionaldehydes, butyraldehydes, acetone, methylethylketone, diethyl ketone. Various aliphatic, cycloaliphatic, aromatic, andheterocyclic amines are also useful providing they contain at least oneamino group having at least one active hydrogen attached thereto.Illustrative of these amines are the monoand dialkylamines, particularlymonoand di-lower alkylamines, such as met'hylamine, ethylamine,propylamine, dodecylamine, methyl ethylamine, diethylamine; thecycloalkylamines such as cyclohexylamine, cyclo-pentylamine, and thelower alkyl-substituted cycloalkylamines such as3-methylcyclohexylamine; 1,4-cyclohexylenediamine; arylamines such asaniline, mono-, di-, and tri-, lower alkyl-substituted phenyl amines,naphthylamines, 1,4-phenylene diamines; lower alkanol amines such asethan-olamine and diethanolamine; alkylene diamines such as ethylenediamine, diethylene triamine, triethylene tetramine, propylene diamines,octamethylene diamines; and heterocyclic amines such as piperazine,4-aminoethylpiperazine, 2-octadecyl-imidazoline; and oxazolidine. Boronacids are also useful conversion agents and include boronic acids (e.g.,alkyl-B(OH) or aryl-B(OH boric acid (i.e., HgBO tetraboric acid,metaboric acid, and esters of such boron acids.

The phosphorus acids are useful conversion agents and include thevarious alkyl and aryl phosphinic acids, phosphinus acids, phosphonicacids, and phosph-onous acids. Phosphorus acids obtained by the reactionof lower alkanols or unsaturated hydrocarbons such as polyisobuteneswith phosphorus oxides and phosphorus sulfides are particularly useful,e.g., P 0 and P S Oxygen, carbon dioxide, air, and various mixtures ofoxygen and carbon dioxide can be used as conversion agents but they arenot particularly suited for the present process due to thepressure-maintaining apparatus required to use them. If employed, it ispreferable to use these conversion agents in combination with one ormore of the foregoing conversion agents. For example, the combination ofwater and carbon dioxide is particularly effective as a conversion agentfor transforming the overbased materials into a colloidal dispersesystem.

As previously mentioned, the overbased materials are single phasehomogeneous systems. However, depending on the reaction conditions andthe choice of reactants in preparing the overbased materials, theresometimes is present in the product insoluble contaminants. Thesecontaminants are normally unreacted basic materials such as calciumoxide, barium oxide, calcium hydroxide, barium hydroxide, or other metalbase materials used as a reactant in preparing the overbased material.It has been found that a more uniform colloidal disperse system resultsif such contaminants are removed prior to homogenizing the overbasedmaterial with the conversion agents. Obviously a more uniform dispersesystem makes it possible to achieve reproducability of properties inresinous compositions containing such systems. Accordingly, it isprefered that any insoluble contaminants in the overbased materials beremoved prior to converting the material in the colloidal dispersesystem. The removal of such contaminants is easily accomplished byconventional techniques such as filtration or centrifugation. It shouldbe understood however, that the removal of these contaminants, whiledesirable for reasons just mentioned, is not an absolute essentialaspect of the invention and useful products can be obtained whenoverbased materials containing insoluble contaminants are converted tothe colloidal disperse systems.

The conversion agents or a proportion thereof may be retained in thecolloidal disperse system. The conversion agents are however, notessential components of these disperse systems and it is usuallydesirable that as little of the conversion agents as possible beretained in the disperse systems. Since these conversion agents do notreact with the overbased material in such a manner as to be permanentlybound thereto through some type of chemical bonding, it is normally asimple matter to remove a major proportion of the conversion agents and,generally, substantially all of the conversion agents. Some of theconversion agents have physical properties which make them readilyremovable from the disperse systems. Thus, most of the free carbondioxide and/or oxygen gradually escape from the disperse system duringthehomogenization process or upon standing thereafter. Since the liquidconversion agents are generally more volatile than the remainingcomponents of the disperse system, they are readily removable byconventional devolatilization techniques, e.g., heating, heating atreduced pres sures, and the like. For this reason, it may be desirableto select conversion agents which will have boiling points 15 which arelower than the remaining components of the disperse system. This isanother reason why the lower alkanols, mixtures thereof, and loweralkanol-water mixtures are preferred conversion agents.

Again, it is not essential that all of the conversion agent be removedfrom the disperse systems. In fact, useful disperse systems foremployment in the resinous compositions of the invention result withoutremoval of the conversion agents. However, from the standpoint ofachieving uniform results, it is generally desirable to remove theconversion agents, particularly where they are volatile. In some cases,the liquid conversion agents may facilitate the mixing of the collodialdisperse system with the polymeric resin material. In such cases, it isadvantageous to permit the conversion agents to remain in the dispersesystem until it is mixed with the polymeric resin. Thereafter, theconversion agents can be removed from the mixture of the disperse systemand polymeric resins by conventional devolatilization techniques ifdesired.

To better illustrate the colloidal disperse systems produced by theprocess of this invention, a preferred system is described below. It isprepared according to the process of applicants earlier applicationsmaintained hereinbefore.

THE OVERBASED MATERIAL As stated above, the essential materials forpreparing an overbased product are (l) the organic material to beoverbased, (2) an inert, non-polar organic solvent for the organicmaterial, (3) a metal base, (4) a promoter, and an acidic material. Inthis example, these materials are (1) calcium petrosulfonate, (2)mineraloil, (3) calcium hydroxide, (4) a mixture of methanol, isobutanol, andn-pentanol, and (5) carbon dioxide.

A reaction mixture of 1305 grams of calcium sulfonate having a metalratio of 2.5 dissolved in mineral oil, 220 grams of methyl alcohol, 72grams of isobutanol, and 38 grams of n-pentanol is heated to 35 C. andsubjected to the following operating cycle four times; mixing with 143grams of 90% calcium hydroxide and treating the mixture with carbondioxide until it has a base number of 32-39. The resulting product isthen heated to 155 C. during a period of 9 hours to remove the alcoholsand then filtered at this temperature. The filtrate is a calciumoverbased petrosulfonate having a metal ratio of 12.2.

CONVERSION TO A COLLOIDAL DISPERSE SYSTEM A mixture of 150 parts of theoverbased material, parts of methyl alcohol, 10.5 parts of n-pentanoland 45 parts of water is heated under reflux conditions at 71-74 C. for13 hours. The mixture becomes a gel. It is then heated to 144 C. over aperiod of 6 hours and diluted with 126 parts of mineral oil having aviscosity of 2000 S'US at 100 F. and the resulting mixture heated at 144C. for an additional 4.5 hours with stirring. This thickened product isa colloidal disperse system of the type contemplated by the presentinventon. As exemplifled hereafter, this conversion mixture also can beconverted using the elongated heating tube of the present invention.

The disperse systems of the invention are characterized by threeessential components: (A) solid, metal-containing particles formed insitu, (B) an inert, non-polar, organic liquid which functions as thedisperse medium, and (C) an organic compound which is soluble in thedisperse medium and the molecules of which are characterized by ahydrophobic portion and at least one polar substituent. In the colloidaldisperse system described immediately above, these components are asfollows: (A) calcium carbonate in the form of solid particles, (B)mineral oil, and (C) calcium petrosulfonate.

From the foregoing example, it is apparent that the solvent for thematerial which is overbased becomes the colloidal disperse medium or acomponent thereof. Of course, mixtures of other inert liquids can besubstituted for the mineral oil or used in conjunction with the mineraloil prior to forming the overbased material. Moreover, after theoverbased material is prepared, additional liquid material, e.g., aplasticizer for the resin can be added if desired to form a part of thedisperse medium.

It is also readily seen that the solid, metal-containing particlesformed in situ possess the same chemical composition as would thereaction products of the metal base and the acidic material used inpreparing the overbased materials. Thus, the actual chemical identity ofthe metal containing particles formed in situ depends upon both theparticular metal base or bases employed and the particular acidicmaterial or materials reacted therewith. For example, if the metal baseused in preparing the overbased material were barium oxide and if theacidic material was a mixture of formic and acetic acids, themetal-containing particles formed in situ would be barium formates andbarium acetates.

However, the physical characteristics of the particles formed in situ inthe conversion step are quite different from the physicalcharacteristics of any particles present in the homogeneous,single-phase overbased material which is subjected to the conversion.Particularly, such physical characteristics as particle size andstructure are quite different. The solid, metal-containing particles ofthe colloidal disperse systems are of a size sufiicient for detection byX-ray diffraction. The overbased material prior to conversion are notcharacterized by the presence of these detectable particles.

X-ray diffraction and electron microscope studies have been made of bothoverbased organic materials and colloidal disperse systems preparedtherefrom. These studies establish the presence in the disperse systemsof the solid, metal-containing salts. For example, in the dispersesystem prepared hereinabove, the calcium carbonate is present as solidcalcium carbonate having a particle size of about 40 to 50 A. (unitparticle size) and interplanar spacing (dA.) of 3.035. But X-raydiffraction studies of the overbased material from which it was preparedindicate the absence of calcium carbonate of this type. In fact, calciumcarbonate present as such, if any, appears to be amorphous and insolution. While applicant doe not intend to be bound by any theoryoffered to explain the changes which accompany the conversion step, itappears that conversion permits particle formation and growth. That is,the amorphous, metal-containing apparently dissolved salts or complexespresent in the overbased material form solid, metal-containing particleswhich by a process of particle growth become colloidal particles. Thus,in the above example, the dissolved amorphous calcium carbonate salt orcomplex is transformed into solid particles which then grow. In thisexample, they grow to a size of 40 to 50 A. In many cases, theseparticles apparently are crystallites. Regardless of the correctness ofthe postulated mechanism for in situ particle formation the fact remainsthat no particles of the type predominant in the disperse systems arefound in the overbased materials from which they are prepared.Accordingly, they are unquestionably formed in situ during conversion.

As these solid metal-containing particles formed in situ come intoexistence, they do so as pre-wet, pre-dispersed solid particles whichare inherently uniformly distributed throughout the other components ofthe disperse system. The liquid disperse medium containing these pre-wetdispersed particles is readily incorporated into various othercompositions thus facilitating the uniform distribution of theparticles. This pre-wet, pre-dispersed character of the solidmetal-containing particles resulting from their in situ formation is,thus, an extremely important feature of the disperse system.

In the foregoing example, the third component of the disperse system(i.e., the organic compound which is soluble in the disperse medium andwhich i characterized by molecules having a hydrophobic portion and apolar substituent) is calcium petrosulfonate,

wherein R is the residu of the petrosulfonic acid. In this case, thehydrophobic portion of the molecule is the hydrocarbon moiety ofpetrosulfonic, i.e., R The polar substituent is the metal salt moiety,

0 H H fiOCaO-S| o 0 The hydrophobic portion of the Organic compound is ahydrocarbon radical or a substantially hydrocarbon radical containing atleast about twelve aliphatic carbon atoms. Usually the hydrocarbonportion is an aliphatic or cycloaliphatic hydrocarbon radical althoughaliphatic or cycloaliphatic substituted aromatic hydrocarbon radicalsare also suitable. In other words, the hydrophobic portion of theorganic compound is the residue of the organic material which isoverbased minus its polar substituents. For example, if the material tobe overbased is a carboxylic acid, sulfonic acid, or phosphorus acid,the hydrophobic portion is the residue of these acids which would resultfrom the removal of the acid functions. Similarly, if the material to beoverbased is a phenol, a nitrosubstituted polyolefin, or an amine, thehydrophobic portion of the organic compound is the radical resultingfrom the removal of the hydroxyl, nitro, or amino group respectively. Itis the hydrophobic portion of the molecule which renders the organiccompound soluble in the solvent used in the overbasing process and laterin the disperse medium.

Obviously, the polar portion of these organic compounds are the polarsubstituents such as the acid salt moiety discussed above. When thematerial to be overbased contains polar substituents which will reactwith the basic metal compound used in overbasing, for example, acidgroups such as carboxy, sulfino, hydroxysulfonyl, and phosphorus acidgroups or hydroxyl groups, the polar substituent of the third componentis the polar group formed from the reaction. Thus, the polar substituentis the corresponding acid metal salt group or hydroxyl group metalderivative, e.g., an alkali or alkaline earth metal sulfonate,carboxylate, sulfinate, alcoholate, or phenate.

On the other hand, some of the materials to be overbased contained polarsubstituents which ordinarily do not react with metal bases. Thesesubstituents include nitro, amino, ketocarboxyl, carboallroxy, etc. Inthe disperse systems derived from overbased materials of this type thepolar substituents in the third component are unchanged from theiridentity in the material which was originally overbased.

The identity of the third essential component of the disperse systemdepends upon the identity of the starting materials (i.e., the materialto be overbased and the metal base compound) used in preparing theoverbased material. Once the identity of these starting materials isknown, the identity of the third component in the colloidal dispersesystem is automatically established. Thus, from the identity of theoriginal material, the identity of the hydrophobic portion of the thirdcomponent in the disperse system is readily established as being theresidue of that material minus the polar substituents attached thereto.The identity of the polar substituents on the third component isestablished as a matter of chemistry. If the polar groups on thematerial to be overbased undergo reaction with the metal base, forexample, if they are acid functions, hydroxy groups, etc., the polars-ubstituent in the final product will correspond to the reactionproduct of the original substituent and the metal base. On the otherhand, if the polar substituent in the material to be overbased is onewhich does not react with metal bases, then the polar substituent of thethird component is the same as the original substituent.

As previously mentioned, this third component can orient itself aroundthe metal-containing particles to form micellar colloidal particles.Accordingly, it can exist in the disperse system as an individual liquidcomponentdissolved in the disperse medium or it can be associated withthe metal-containing particles as a component of micellar colloidalparticles.

The following examples illustrate the preparation of typical overbasedorganic materials useful as starting ma terials in the process of thisinvention. A A

Example 1 To a mixture of 400 parts (by weight) of a 30% mineral oilsolution of barium petroleum sulfonate (sulfate ash of 7.6%), 32.5 partsof octyl phenol, and 197 parts of Water, there is added 73 parts ofbarium oxide within a period of 30 minutes at 5784 C. The mixture isheated at C. for 1' hour to remove substantially all of the water and isthen blown with 75 parts of carbon dioxide at 133170 C. Within a periodof 3 hours. A mixture of 1000 grams of the above carbonated intermediateproduct and 121.8 parts of octyl phenol and 234 parts of bariumhydroxide is heated at 100C. and then at 150 C. for one hour. Themixture is then blown with carbon dioxide at 150 C. for one hour at arate of 3 cubic ft. per hour. The carbonated product, i.e., theoverbased organic material, is filtered and the filtrate is found tohave a sulfate ash content of 39.8% and a metal ratio of 9.3.

Example 2 To a mixture of 3245 grams (12.5 equivalents) of bariumpetroleum sulfonate, 1460 grams (7.5 equivalents) of heptyl phenol, and2100 grams of water in 8045 grams of mineral oil there is added at 82C., 7400 grams (96.5 equivalents) of barium oxide. The addition ofbarium oxide causes the temperature to rise to C. which temperature ismaintained until all of the water has been distilled. The mixture thenis blown with carbon dioxide until it is substantially neutral. Thepro-duct is diluted with 5695 grams of mineral oil and filtered. Thefiltrat e'is found to have a barium sulfate ash content -of 30.5% and ametal ratio of 8.1.

Example 3 A mixture of 1285 grams (1.0 equivalent) of 40 percent bariumpetroleum sulfonate and 400 grams(12l5 equivalents) of methanol isstirred at 5560 C. while 301 grams (3.9 equivalents) of barium oxide isadded po-rtionwise over a period of one hour. The mixture is stirred anadditional two hours at 4555 C., then treated with carbon dioxide at 5565" C. for two hours. The resulting mixture is freed of methanol b'yheatingto C. The residue is filtered through a siliceous filter aid, theclear brown filtrate showing the analyses: sulfate ash, 33.2%, neut.no., slightly acid; metal ratio, 4.7.

Example 4 A solution of .1928 grams (1.5 equivalent) of 40 percentbarium petroleum sulfonate in 1004 grams of oil and 150 grams (4.7equivalents of methanol is prepared and heated to 40 C. Carbon dioxideis bubbled into this solution of 796 grams (10.4 equivalents) of bariumoxide is added por'tionwise over a period of two hours. The temperatureis maintained between 40 C. and 70 C. throughout and when all the bariumoxide has been added the carbon dioxide-treatment is continued for'anadditional four hours. The resulting mixture is then heated to 150 C.and held at this temperature for 30 minutes to remove any volatilematerial. The residue is filtered, yielding a clear, brown filtratehaving the following analyses: sulfate ash, 32.5%; neut. 110., 1.2(basic); metal ratio, 7:2.

19 Example A stirred mixture of 57 grams (0.4 equivalent) of nonylalcohol and 301 grams (3.9 equivalents) of barium oxide is heated at150-175 C. for an hour, then cooled to 80 C. whereupon 400 grams (1.2.5equivalents) of methanol is added. The resultant mixture is stirred at7075 C. for 30 minutes, then treated with 1285 grams (1.0 equivalent) of40 percent barium petroleum sulfonate. This mixture is stirred at refluxtemperature for an hour, then treated with carbon dioxide at -60-70 C.for two hours. The mixture then is heated to 160 C. 0/18 mm. andfiltered. The filtrate is a clear, brown oil having the followinganalyses: sulfate ash, 32.5%; neut. no., nil; metal ratio, 4.7.

Example 6 A mixture of 574 grams (0.5 equivalent) of 40 percent bariumpetroleum sulfonate, 98 grams (1.0 equivalent) of furfuryl alcohol, and762 grams of mineral oil is'heated with stirring at 100 C. for an hour,then treated portionwise over a 15-minute period with 230 grams (3.0equivalents) of barium oxide. During this latter period the temperaturerises to 120 C. (because of the exothermic nature of the reaction ofbarium oxide and the alcohol); the mixture then is heated at 150-160 C.for an hour, and treated subsequently at this temperature for 1.5 hourswith carbon dioxide. The material is concentrated by heating to a finaltemperature of 150 C./ mm. then filtered to yield a clear, oil-solublefiltrate having the following analyses: sulfate ash, 21.4%; neut. no.,2.6 (basic); metal ratio, 6.1.

Example 7 To a mixture of 1145 grams of a mineral oil solution of a 40percent solution of barium mahogany sulfonate (1.0 equivalent) and 1100grams of methyl alcohol at 55 C. there is added 220 grams of bariumoxide while the mixture is being blown with carbon dioxide at a rate of2-3 cubic feet per hour. To this mixture there is added an additional 78grams of methyl alcohol and then 460 grams of barium oxide while themixture is being blown with carbon dioxide. The carbonated product isheated to 150 C. for one hour and filtered. The filtrate is found tohave a barium sulfate ash content of 53.8 percent and a metal ratio of8.9.

Example 8 A carbonated basic metal salt is prepared in accordance withthe procedure of Example 7 except that a total of equivalents .of bariumoxide is used per equivalent of the barium mahogany sulfonate used. Theproduct is found to have a metal ratio of 13.4.

Example 9 A mixture of 520 parts (by weight) of a mineral oil, 480 partsof a sodium petroleum sulfonate (molecular weight of 480), and 84 partsof water is heated at 100 C. for-4 hours. The mixture is then heatedwith 86 parts of a 76% equeous solution of calcium chloride and 72 partsof lime (90% purity) at 100 C. for 2 hours, dehydrated by heating to awater content of less than 0.5%, cooled to 50 C., mixed with 130 partsof methyl alcohol, and then blown with carbon dioxide at 50 C. untilsubstantially neutral. The mixture is then heated to 150 C. to distillotf methyl alcohol and water and the resulting oil solution of the basiccalcium sulfonate is filtered. The filtrate is found to have a calciumsulfate ash content of 16% and a metal ratio of 2.5. A mixture of 1305grams of the above carbonated calcium sulfonate, 930 grams of mineraloil, 220 grams of methyl alcohol, 72 grams of isobutyl alcohol, and 38grams of amyl alcohol is prepared, heated to 35 C., and subjected to thefollowing operating cycle 4 times: mixing with 143 grams of 90% calciumhydroxide and treating the mixture with carbon dioxide until it has abase number of 32-39. The

resulting product is then heated to C. during a period of 9 hours toremove the alcohols and then filtered through a siliceous filter-aid atthis temperature. The filtrate has a calcium sulfate ash content of39.5%, and a metal ratio of 12.2.

Example 10 A basic metal salt is prepared by the procedure described inExample 9 except that the slightly basic calcium sulfonate having ametal ratio of 2.5 is replaced with a mixture of that calcium sulfonate(280 parts by weight) and tall oil acids (800 parts by weight, having anequivalent weight of 280) and that the total amount of calcium hydroxideused is 772 parts by weight. The resulting highly basic metal salt ofthe process has a calcium sulfate ash content of 42.3%, a metal ratio of6.25, and an oil content of 38.9%.

Example 1 1 A highly basic metal salt is prepared by the procedure ofExample 10 except that the slightly basic calcium starting materialhaving a metal ratio of 2.5 is replaced with tall oil acids (1250 partsby weight, having an equivalent weight of 340) and the total amount ofcalcium hydroxide used is 772 parts by weight. The resulting highlybasic metal salt has a metal ratio of 5.2, a calcuim sulfate ash contentof 41%, and an oil content of 33%.

Example 12 A highly basic metal salt is prepared by the procedure ofExample 10 except that the slightly basic calcium sulfonate startingmaterial is replaced with a mixture of that basic calcium sulfonate (555parts by weight) and tall oil acids (694 parts by weight having anequivalent weight of 340) and the amount of calcium hydroxide used is772 parts by weight. The resulting metal salt has a metal ratio of 7.9,a calcium sulfate ash content of 45%, and an oil content of 32%.

Example 13 A basic metal salt is prepared by the process of Example 9except that the amount of the slightly basic calcium sulfonate used is1672 parts and the amount of the calcium hydroxide used is 1062 parts.The resulting highly basic metal salt has a metal ratio of 19 and acalcium sulfate ash content of 54.7%.

Example 14 A highly basic metal salt is prepared by the procedure ofExample 13 except that the slightly basic calcium sulfonate startingmaterial has a metal ratio of 1.6 and the amount of this calciumsulfonate used is 1050 parts (by The procedure of Example 9 is repeatedexcept that the sodium petroleum sulfonate is replaced by an equivalentamount of sodium polydodecyl benzene sulfonate. The resulting highlybasic metal salt has a calcium sulfate ash content of 41.5% and a metalratio of 13.1.

A preferred aspect in the formation of the disperse systems by theprocess of this invention is that the overbased organic material besubstantially free from insoluble contaminants. For example, if anycontaminants are present as a result of insufiicient carbonation of thealkaline earth metal base used in preparing the overbased material, itis preferably filtered or centrifuged before it isused in the process ofthis invention. This is desirable since, unless they are removed, theresulting disperse system will not have the desired degree ofhomogeniety, in most cases.

The concentration of the metal-containing components in the overbasedorganic material preferably should be at least about 10% by weight. Ifthe concentration is below about 10%, a satisfactory disperse systemusually cannot be formed by the process.

When mineral oil is present in the conversion mixture, it is preferablyone having a viscosity value ranging from 50 SUS (Saybolt Universalseconds) at 100 F. to 500 SUS at 210 F. Especially useful is a mineraloil from SAE 5 to SAE 120 grade. The source of the mineral oil is notcritical. A preferred aspect of the invention involves using, as astarting material, an overbased organic material in which, at least aportion of the non-metal containing liquid component is mineral oil.Those overbased organic materials wherein this liquid componentcomprises at least 10% and preferably, at least 25% by weight mineraloil are especially suitable for conversion by the present process.Mineral oil can comprise the entire non-metal containing liquidcomponent.

Additional thickening is desirable where the product formed by theprocess of this invention is to be used as a corrosion inhibitingcomposition. Particularly useful compositions are obtained whencommercial resins are added to the product. Resins which have been founduseful are the hydrocarbon resins which have a softening point of atleast 100 C., and preferably having a softening point range of from100-130 C. Incorporation of such resins into the product results in acoating composition which is firm rather than soft and grease-like. Thischaracteristic of the corrosion inhibiting compositions is desirablebecause it provides resistance to abrasion, dirt, and gravel pick-up,etc.

Examples of the hydrocarbon resins which have been found useful in thecompositions of this invention include coumarone-indenes, polystyrenes,polymerized beta-pinenes, and higher molecular weight polyisobutylenes.Obviously, the resins chosen to be added to a particular compositionmust be miscible with the composition and soluble in any solvent used inthe preparation.

The following examples illustrate the process for the preparation of thecolloid disperse systems according to the process of this invention.

Example A Thirty-two parts of a primary amyl alcohol, 64 parts of methylalcohol, 800 parts of the overbased organic material of Example 9, areintroduced into mixing tank No. 2 through line 1 in the order namedwhile mixing With stirrer 3. Eighty parts of water is introduced to themixing tank 2 with mixing in 5 minutes. The valve in line 4 is openedand the mixture is pumped during 55 minutes at 8.5 parts per minute and225260 p.s.i.g. as determined by the back pressure regulator 16, throughthe heating zone 13, consisting of 240 ft. of inch, jacketed steel pipe,heated with 171 C. steam. The heated product mixture is discharged fromthe heating zone 13 through line 14 into the receiver tank 18 containing300 parts of a mineral oil having a viscosity of 2000 SUS at 100 F. Themixture in the receiving tank 19 is heated at 148153 C. for 1 hour whilenitrogen at 13 parts per hr. is introduced via the submerged line 33.The distillate from the condenser 25 is collected in receiver 27. Thedisperse system is of a grease-like consistency containing 6.76%calcium, and 43.9% of the 2000 S-US mineral oil.

Example B A solution of 103 parts of a commercial polystyrene resinhaving a softening point range of 110120 C. in 650 parts of theoverbased organic material of Example 9, 52 parts of methyl alcohol, 26parts of primary amyl alcohol, and 65 parts of water, are introducedinto the mixing tank 2 through line 1 in the order named mixing withstirrer 3, at 38 C. After thorough mixing, the mixture is pumped during62 minutes at 9.6 parts per minute and 250 p.s.i.g. as determined byback pressure regulator 16 through the heating zone 13, consisting of240 feet of inch, jacketed steel pipe, heated with 171 C. steam.

The heated product mixture is discharged from the heating zone 13through line 14 into the receiver tank 19 containing 72 parts of apetroleum naphtha having a boiling Example C In the feed tank 2, 700parts of the overbased organic material of Example 9, 56 parts of methylalcohol, 28 parts of primary amyl alcohol, and 42 parts of water arethoroughly mixed by stirrer 3. The mixture is pumped at 10 parts perminute during 75 minutes under a pressure of 259 p.s.i.g. to the heatingzone 13, consisting of 18 feet of inch jacketed pipe, heated with 167 C.steam. The heated reaction mixture is discharged from the heating zone13 through line 14 into the receiver tank 19 containing 400 parts of amineral oil having a viscosity of 2000 SUS at100 F. The mixture in thereceiver tank 19 is heated to l49- C. while nitrogen at the rate of 2parts per hour is introduced via the submerged line 33. An additional236 parts of 2000 SUS oil is added with mixing. The product is anon-Newtonian collodial disperse system containing 50% of the 2000 SUSmineraloil.

Exam le D A combination of 393 parts of the overbased material ofExample 13, 107 parts of mineral oil having a viscosity of 100 SUS, 40parts of methyl alcohol, 20 parts of primary amyl alcohol, and 75 partsof water is charged to the feed tank 2 and mixed with mixer 3. Themixture is pumped at 20 parts per minute for 30 minutes at 240 p.s.i.g.through the heating zone 13, consisting of 18 feet of inch jacketed pipeheated with 171 Cl'steam. The heated product mixture is discharged fromthe heating zone 13 through line 14 into the receiver tank 19 containing400 parts of .a mineral oil having a viscosity of 2000 SUS. The mixturein the receiver tank is heate'd to 145, C. 'with nitrogen at 2 parts perhr. introduced via submerged line 33. An additional 72 parts of oilhaving a viscosity of 2000 SUS is added and thoroughly mixed yielding afinal product containing 50% of the 2000 SUS mineral oil.

Example E A grease composition is prepared according to the procedure ofExample A except that 700 parts of the overbased organic material ofExample 1 is used in place of that of Example 9. The resulting productis a grease-like non-Newtonian colloidal disperse system.

Example F A composition having a grease-like consistency is formed bythe process of Example A except that 700 parts of the overbased organicmaterial of Example 14 is used in lieu of that of Example 9.

Example G In the feed tank 2, 800 parts of the overbased organicmaterial of Example 10', 800 parts of a mineral oil having a viscosityof 2000 SUS at 100 F., and parts of acetic acid are mixed by stirrer 3.The mixture is pumped at 15 parts per minute for minutes under apressure of p.s.i.g. through the heating zone 13, consisting of 18 feetof 4 inch jacketed pipe, heated with 121 C. steam. The gelled product isdischarged from heating zone 13 through line 14 into the receiving tank19 Where it is mixed with 400 parts of a petroleum naphtha having aboiling range of 156-193 C. The mixture in receiving tank 19 is heatedto 193 C. in 3 hours while nitrogen is introduced at 2 parts per hourthrough submerged line 33. The distillate 23 from the condenser 25 iscollected in receiver 27. The product is grease-like in consistency.

By substituting other overbased organic materials and conversion agentsin the indicated proportions, as discussed supra, for those utilized inExamples AG, the correspond ing non-Newtonian colloidal diperse systemscan be prepared according to the process of the present invention. Forexample, by treating conversion mixtures of the earlier filedapplications and patent mentioned hereinabove in the manner required bythe present process and exemplified above, other colloidal dispersesystems can be prepared.

What is claimed is:

1. A process for converting a member selected from the class consistingof alkali and alkaline earth metal overbased organic materials having ametal ratio of at least about 3.5, said material comprising at leastabout 30% by weight of non-metalv containing liquid medium, into anon-Newtonian colloidal disperse system comprising passing a mixture of(1) an overbased material and (2) from about 1% to about 80% by weightbased on the weight of said overbased organic material excluding theweight of the liquid medium of a conversion agent selected from theclass consisting of water, lower aliphatic carboxylic acids, alcohols,phenols, ketones, aldehydes, amines, boron acids, and phosphorus acids,through an elongated heating zone under a pressure above about oneatmosphere and sufiicient to maintain the mixture in the liquid state ata temperature within the range of from about 90 C. to about 320 C. atsuch a rate that an increment of said mixture is in the heating zone forsufficient time to permit conversion to take place.

2. A process according to claim 1 wherein said overbased material is aliquid solution containing from about 10% to about 70% by weight ofmetal-containing components.

3. A process according to claim 2 wherein the conversion agent isselected from the class consisting of lower aliphatic carboxylic acidshaving from 1 to 8 carbon atoms, water, andwater-alcohol mixtures.

4. A process according to claim 3 wherein the overbased material is acarbonated, alkaline earth metal overbased organic acid.

5. The process according to claim 4 wherein the liquid medium isselected from the class consisting of mineral oil and mixtures ofmineral oil with mineral oil-miscible inert organic solvents.

6. The process according to claim 5 wherein the over- 24 based organicmaterials have a metal ratio of from 4.5 to about 20.

7. The process of claim 6 wherein the alkaline earth metal overbasedacid is a calcium overbased acid.

8. The process of claim 5 wherein the alkaline earth metal overbasedacid is a barium overbased acid.

9. The process of claim 6 wherein the acid is an oilsoluble sulfonicacid.

10. The process of claim 5 wherein the acid is an oilsoluble carboxyiicacid.

11. The process of claim 6 wherein the acid is a mixture of oil-solublesulfonic and carboxylic acids.

12. The process of claim 6 wherein the alcohol portion of thewater-alcohol mixture is a mixture of lower alkanols.

13. The process of claim 6 wherein the alcohol of the water-alcoholmixture is a mixture of at least two alkanols selected from the class ofmethyl alcohol, ethyl alcohol, propyl alcohols, butyl alcohols, andpentyl alcohols.

14. The process of claim 6 wherein the conversion agent is acetic acid.

15. The process comprising:

(A) forming a mixture of (1) an overbased organic material comprising afluid mineral oil solution containing from about 30% to about by weightof carbonated, calcium overbased sulfonic acid having at least about 12aliphatic carbon atoms and characterized by a metal ratio of from about8 to about 20; and (2) from about 1% to about based on the weight ofsaid overbased organic material exclusive of the mineral oil of awater-lower alkanol mixture.

(B) passing said mixture through an elongated heating zone under apressure above about one atmosphere and suflicient to maintain themixture in the liquid state at a temperature within the range of fromabout C. to about 320 C. at such a rate that an increment of saidmixture is in the heating zone for sufficient time to permit conversionto take place.

References Cited UNITED STATES PATENTS 2,948,679 8/1960 Rees et al.252-28 DANIEL E. WYMAN, Primary Examiner.

I. VAUGHN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,377,283 April 9, 1968 Richard L- McMillen It is certified that errorappears in the above identified patent and that said Letters Patent arehereby correct-ed as shown below:

Column 1, line 53, "subequent" should read subsequent line 58, after"1967" insert applicant discloses other colloidal disperse systems andprocesses for their preparation Column 2, line 41, "phosphoric" shouldread phosphorus line 42, "above one" should read above about one line64, "vale 12" should read valve 12 Column 4, line 31, "non-Newtonial"should read non-Newtonian Column 6, line 58, "1,2-dibrome" should read1,2-dibromo line 75, "alkylated benzers" should read alkylated benzenesColumn 7, line 75, "enert" should read inert Column 8, line 55,"2,856,360" should read 2,859,360 line 75, "employ" should read employedColumn 10, line 13, "nitrict" should read nitric line 29, "armorphous"should read amorphous line 37, "a complex" should read complex line 46,"remainedr" should read remainder Column 11, line 32, "acide" shouldread acid Column 12, line 46, "system" should read systems Column 13,line 34, "monoethylether" should read monomethylether Column 15, line59, "inventon" should read invention line 65, "in situ" should read insitu in italics. Column 16, lines 9, l3, 19, 22, 57, 61,

62 70 and 71 "in situ", each occurrence should read in situ in italics.Column 17, line 6, "residu" should read residue Column 18, line 22, "170C." should read 170 C. line 63, "(4.7 equivalents of" should read [4.7equivalents) of Column 19, line 59, "equeous" should read aqueous Column20, line 21, "calcium" should read calcium sulfonate line 27, "cuim"should read cium Column 24, line 1, "from 4.5" should read from about4.5 line 18, "class of" should read class consisting of Signed andsealed this 25th day of November 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attestlng OfficerCommissioner of Patents

